CN112337499B - Composite nano material with catalytic property, preparation method and application - Google Patents
Composite nano material with catalytic property, preparation method and application Download PDFInfo
- Publication number
- CN112337499B CN112337499B CN202011316506.5A CN202011316506A CN112337499B CN 112337499 B CN112337499 B CN 112337499B CN 202011316506 A CN202011316506 A CN 202011316506A CN 112337499 B CN112337499 B CN 112337499B
- Authority
- CN
- China
- Prior art keywords
- dimensional
- composite
- catalytic
- mofs
- nano
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 73
- 239000002131 composite material Substances 0.000 title claims abstract description 52
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 229920001690 polydopamine Polymers 0.000 claims abstract description 45
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 34
- 239000000463 material Substances 0.000 claims abstract description 32
- 239000002135 nanosheet Substances 0.000 claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 7
- 239000002184 metal Substances 0.000 claims abstract description 7
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 3
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 22
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- 239000011148 porous material Substances 0.000 claims description 20
- 239000002245 particle Substances 0.000 claims description 16
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 14
- 238000003763 carbonization Methods 0.000 claims description 13
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 claims description 11
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 11
- 229960003638 dopamine Drugs 0.000 claims description 11
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000012377 drug delivery Methods 0.000 claims description 7
- 229910021645 metal ion Inorganic materials 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 238000010000 carbonizing Methods 0.000 claims description 4
- 102000004169 proteins and genes Human genes 0.000 claims description 4
- 108090000623 proteins and genes Proteins 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 3
- 229910002444 Co–Nx Inorganic materials 0.000 claims description 2
- 229910021536 Zeolite Inorganic materials 0.000 claims description 2
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 238000011049 filling Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000001990 intravenous administration Methods 0.000 claims description 2
- 102000039446 nucleic acids Human genes 0.000 claims description 2
- 108020004707 nucleic acids Proteins 0.000 claims description 2
- 150000007523 nucleic acids Chemical class 0.000 claims description 2
- 229920001184 polypeptide Polymers 0.000 claims description 2
- 102000004196 processed proteins & peptides Human genes 0.000 claims description 2
- 108090000765 processed proteins & peptides Proteins 0.000 claims description 2
- 230000002685 pulmonary effect Effects 0.000 claims description 2
- 238000006479 redox reaction Methods 0.000 claims description 2
- 230000000630 rising effect Effects 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 239000010457 zeolite Substances 0.000 claims description 2
- -1 zeolite imidazole ester Chemical class 0.000 claims description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims 2
- 230000009920 chelation Effects 0.000 claims 1
- 239000002105 nanoparticle Substances 0.000 abstract description 8
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 11
- 102000004190 Enzymes Human genes 0.000 description 10
- 108090000790 Enzymes Proteins 0.000 description 10
- 238000006555 catalytic reaction Methods 0.000 description 9
- 238000011160 research Methods 0.000 description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 8
- 102000003992 Peroxidases Human genes 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 108040007629 peroxidase activity proteins Proteins 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 238000010586 diagram Methods 0.000 description 6
- 239000012452 mother liquor Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 238000011068 loading method Methods 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 4
- 239000003814 drug Substances 0.000 description 4
- 239000002149 hierarchical pore Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000002835 absorbance Methods 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000001338 self-assembly Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 102000000546 Apoferritins Human genes 0.000 description 2
- 108010002084 Apoferritins Proteins 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 206010028980 Neoplasm Diseases 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 238000003745 diagnosis Methods 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000001632 sodium acetate Substances 0.000 description 2
- 235000017281 sodium acetate Nutrition 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- IVLXQGJVBGMLRR-UHFFFAOYSA-N 2-aminoacetic acid;hydron;chloride Chemical compound Cl.NCC(O)=O IVLXQGJVBGMLRR-UHFFFAOYSA-N 0.000 description 1
- 239000011165 3D composite Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 102000016938 Catalase Human genes 0.000 description 1
- 108010053835 Catalase Proteins 0.000 description 1
- 229910020676 Co—N Inorganic materials 0.000 description 1
- MWWSFMDVAYGXBV-RUELKSSGSA-N Doxorubicin hydrochloride Chemical compound Cl.O([C@H]1C[C@@](O)(CC=2C(O)=C3C(=O)C=4C=CC=C(C=4C(=O)C3=C(O)C=21)OC)C(=O)CO)[C@H]1C[C@H](N)[C@H](O)[C@H](C)O1 MWWSFMDVAYGXBV-RUELKSSGSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 108010044467 Isoenzymes Proteins 0.000 description 1
- 102000019197 Superoxide Dismutase Human genes 0.000 description 1
- 108010012715 Superoxide dismutase Proteins 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- NUSORQHHEXCNQC-UHFFFAOYSA-N [Cu].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 Chemical compound [Cu].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 NUSORQHHEXCNQC-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 230000008827 biological function Effects 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000012718 coordination polymerization Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000000502 dialysis Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 229960002918 doxorubicin hydrochloride Drugs 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- JBFYUZGYRGXSFL-UHFFFAOYSA-N imidazolide Chemical compound C1=C[N-]C=N1 JBFYUZGYRGXSFL-UHFFFAOYSA-N 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000010413 mother solution Substances 0.000 description 1
- 239000002057 nanoflower Substances 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 230000004962 physiological condition Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 150000008442 polyphenolic compounds Chemical class 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- 150000004032 porphyrins Chemical class 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K45/00—Medicinal preparations containing active ingredients not provided for in groups A61K31/00 - A61K41/00
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
- A61K47/30—Macromolecular organic or inorganic compounds, e.g. inorganic polyphosphates
- A61K47/34—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polyesters, polyamino acids, polysiloxanes, polyphosphazines, copolymers of polyalkylene glycol or poloxamers
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
- A61K47/50—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient the non-active ingredient being chemically bound to the active ingredient, e.g. polymer-drug conjugates
- A61K47/69—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient the non-active ingredient being chemically bound to the active ingredient, e.g. polymer-drug conjugates the conjugate being characterised by physical or galenical forms, e.g. emulsion, particle, inclusion complex, stent or kit
- A61K47/6949—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient the non-active ingredient being chemically bound to the active ingredient, e.g. polymer-drug conjugates the conjugate being characterised by physical or galenical forms, e.g. emulsion, particle, inclusion complex, stent or kit inclusion complexes, e.g. clathrates, cavitates or fullerenes
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P35/00—Antineoplastic agents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Pharmacology & Pharmacy (AREA)
- Materials Engineering (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Medicinal Chemistry (AREA)
- Epidemiology (AREA)
- General Chemical & Material Sciences (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Bioinformatics & Cheminformatics (AREA)
- Proteomics, Peptides & Aminoacids (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention belongs to the field of synthesis of nano materials, and particularly relates to a composite nano material with catalytic property and a preparation method thereof. The invention provides a composite nano material with catalytic property, which is a metal organic framework-polydopamine hybrid nano particle with a three-dimensional structure, which is obtained by assembling a two-dimensional nano sheet formed by a metal organic framework material as a basic unit and polydopamine as a cross-linking agent with the two-dimensional nano sheet, and is carbonized at high temperature to obtain the catalytic property.
Description
Technical Field
The invention belongs to the field of synthesis of nano materials, and particularly relates to a composite nano material with catalytic property and a preparation method thereof.
Background
Nanoenzymes are nanomaterials that catalyze enzyme-like reactions under physiological conditions, and have properties such as high catalytic activity and precise substrate specificity, and play an important role in biochemical monitoring, disease diagnosis, tumor diagnosis, oxidation resistance, antibiosis, environmental treatment, and the like (Advanced Materials, volume 31, page 1902885, 2019). Early researches on nanoenzymes mostly made of non-porous materials such as iron oxide and ruthenium oxide, and limited surface area seriously hinders the activity of enzymes.
In recent years, metal-organic frameworks (MOFs) have been widely used in the fields of adsorption, separation, chemical detection, gas storage, catalysis, sensing, etc. due to their properties such as controllable pore size or shape, and extremely high porosity and surface area. Wherein, the iron or copper porphyrin MOFs can be used as peroxidase-like enzyme in the field of catalysis. Compared with solid non-porous nano materials, the MOFs has ordered ion and ligand arrangement and micropore channels, and can provide a higher specific surface area. However, the pore size of the MOFs material is much smaller than 2nm, the active sites are not fully exposed and the mass transfer diffusion is limited, thereby affecting the application performance of the MOFs material as a nano enzyme material.
Research shows that the original structure and partial properties can be retained by pyrolyzing MOFs derivative materials, and monatomic catalytic sites can be obtained to simulate the activity of various enzymes such as allozymes, catalase and superoxide dismutase (ACS Catalysis, volume 10, pages 6579-6586, 2020). However, in catalytic applications involving free radicals, a large number of sites within the material do not function adequately due to limitations in free radical lifetime and diffusion distance.
The key point of improving the catalytic activity of the MOFs material is to regulate and control the pore size and the morphology of the MOFs material. Research has shown that the coordination polymerization of MOFs can be interfered by the flexible, plastic and processable properties of the polymer to regulate the growth and properties (Chemical Reviews, volume 120, pages 8267-8302, 2020). By utilizing the characteristics, the nanometer material with larger aperture can be prepared theoretically. However, the currently reported related researches mainly focus on the hierarchical pore structure of mesopores and micropores, and the researches of applying the MOFs materials to nanoenzymes by a carbonization method have not been reported.
In summary, the catalytic activity of the MOFs material can be improved to a certain extent by regulating the pore size and the morphology of the MOFs material, but the utilization rate of the internal catalytic active sites of the MOFs material needs to be improved. Two-dimensional nanomaterials (e.g., graphene oxide) have abundant surface functional groups that can provide a large number of active centers on the surface. However, two-dimensional nanomaterials aggregate easily, which greatly limits their performance in practical applications. Researches show that the hydrogen bond effect between two-dimensional nano sheets is overcome, the two-dimensional nano sheets are assembled into a three-dimensional (3D) structure by utilizing the coordination effect between organic and inorganic materials, and the utilization rate of active sites can be effectively improved while the problem of nano sheet re-accumulation is solved (Advanced Science, volume 7, page 1903077, 2020).
The polydopamine has the characteristics of certain hydrophilicity, adhesion, good biocompatibility and the like. In addition, the surface of the material has a large number of functional groups, especially amino groups and catechol, which provide action sites for binding metal ions. The formation process of the MOF is interfered by the coordination of polydopamine and metal ions, and the MOF is assembled into a three-dimensional structure (nanoflower), so that the problem of re-stacking of the nanosheets is expected to be solved. In addition, the large-size mesoporous space stacked by the two-dimensional structure can also play a role of a carrier for loading functional biomolecules. (Small, volume 14, pages 1800090, 2018).
To sum up, the MOFs nano materials currently have certain limitations in the catalytic application direction, and therefore, new and stable MOFs need to be designed and developed for the field of biomedical catalysis. Accordingly, the present invention is directed to providing a MOFs-PDA composite carbonized nanomaterial having catalytic properties to solve at least one of the above problems.
Disclosure of Invention
In view of the above, the present invention provides a novel composite nanomaterial, and a preparation method and application thereof, so as to solve at least one of the above problems.
One of the purposes of the invention is to provide a composite nano material with catalytic property, and the specific technical scheme is as follows.
The composite nano material is a metal organic framework-polydopamine hybrid nano particle with a three-dimensional structure, which is obtained by assembling a two-dimensional nano sheet formed by a metal organic framework material as a basic unit and polydopamine as a cross-linking agent with the two-dimensional nano sheet, and is carbonized at high temperature to obtain the catalytic property.
Further, the composite nano material can participate in oxidation-reduction reaction and has catalytic activity similar to peroxidase.
Further, the metal organic framework material is ZIF series, MIL series or UIO series.
Further, the composite nano material can catalyze hydrogen peroxide to generate active oxygen under acidic conditions, and the amount of the generated active oxygen is in direct proportion to the concentration of the hydrogen peroxide.
Furthermore, the catalytic active site of the composite nano material is a structure formed by N element and single atom.
Further, the catalytically active sites comprise Zn-Nx and/or Co-Nx.
Preferably, in one embodiment of the present invention, the catalytically active site is Zn-N 4 . It should be noted that the technical solution to implement the present invention is not limited to the disclosure of the embodiment. To stabilize N-coordinated transition metal centers (metal-N) X ) The Co can form a porphyrin Co site with surrounding atoms, so that Co-N can be obtained by carbonization 4 The catalytically active site of (3).
Furthermore, the surface of the composite nano material has a mesoporous structure, and the aperture of the mesoporous structure is 20-50nm.
The aperture is a hierarchical pore structure with coexisting mesopores and micropores, and in the prior art, although a mesopore structure is introduced, micropores are mainly used and mesopores are used as auxiliaries. The aperture of the invention is mainly mesopores with larger size, and the aperture of some macropores exists, and only some micropore structures exist on the two-dimensional nanosheet.
Preferably, in one embodiment of the present invention, the pore size of the mesoporous structure is 40nm.
Further, the shape of the composite nanometer material is particles with flower-shaped structures, and the particle size of the particles is in the range of 50nm-5 microns.
Preferably, in one embodiment of the present invention, the particle size is 200nm.
Further, the specific surface area of the composite nano material is about 300-400m 2 g -1 。
Preferably, in one embodiment of the present invention, the specific surface area is about 388m 2 g -1 . It should be noted that the experimental data in the preferred embodiment of the present invention should be understood as the best technical effect of the present invention, rather than the only technical solution to solve the technical problem of the present invention.
The invention also aims to provide a preparation method.
A preparation method of a composite nano material with catalytic property adopts a two-dimensional nano structure formed by a metal organic framework material as a basic unit, then self-assembles the two-dimensional nano structure to form a three-dimensional structure by utilizing the capability of polydopamine to form a coordinate bond, and finally, the composite nano material is prepared by high-temperature carbonization operation.
Further, the metal organic framework material is ZIF series, MIL series or UIO series.
Further, the ZIF series is a zeolite imidazolate framework material-8, and is synthesized by 2-methylimidazole and zinc nitrate hexahydrate.
Further, the 2-methylimidazole, the zinc nitrate hexahydrate and the dopamine are heated and stirred in a mixed solution of methanol and water to form the two-dimensional nanostructure, and the two-dimensional nanostructure has a mesoporous structure.
Further, the volume ratio of the methanol to the water is 3-5.
As a preference, in one embodiment of the present invention, the volume ratio of methanol to water is 4.51.
Further, the mass ratio of the 2-methylimidazole to the zinc nitrate hexahydrate to the dopamine is 20-40.
As a preference, in one embodiment of the present invention, the mass ratio of the 2-methylimidazole to the zinc nitrate hexahydrate to the dopamine is 32:144:10.
according to the preparation method provided by the invention, a flower-like structure peroxidase with catalytic properties can be prepared under the condition that the mass/volume range ratio of the substances provided by the invention (such as 2-methylimidazole: zinc nitrate hexahydrate: dopamine = 20-40. The experimental data given in the embodiments of the present invention should be understood as the only technical solutions that can achieve the best technical effects, rather than solving the technical problems of the present invention. A flower-like peroxidase with catalytic properties can still be prepared without deviating from the optimal experimental data, but the flower-like morphology and size of the flower-like peroxidase can vary and fluctuate within a certain range, but the variation and fluctuation range is within the size range claimed by the invention (for example, the pore size of the mesoporous structure is 20-50nm; the particle size of the particles is 50nm-5 μm).
Further, the high-temperature carbonization operation is to reach the final temperature of 800 ℃ at the temperature rising speed of 5-10 ℃/min under the condition of filling nitrogen, and to carbonize for 1-2h, so as to obtain the composite carbonized nanomaterial with catalytic property. By a high-temperature carbonization method, the pore diameter of the MOF material can be increased, and an atomic-scale metal catalyst can be obtained, but the synthesis process of the hierarchical pore MOF is extremely complex, and the synthesis controllability and repeatability are technical difficulties needing to be broken through at present. According to the preparation method provided by the invention, the two-dimensional nano material is assembled into the three-dimensional material through the adhesion and chelating coordination of polydopamine, so that the nano material with large aperture is obtained, the preparation method is simple, convenient and controllable, and the active sites are fully exposed through a carbonization means, so that the nano material with large aperture, which integrates the functions of catalysis and loading of guest molecules, is prepared.
Further, the obtained composite nano material is flower-shaped structure particles, and the particle size range of the particles is 50nm-5 mu m; the specific surface area is about 300-400m 2 g -1 。
The preparation method provided by the invention firstly adopts a one-pot method, and utilizes the difference of coordination/polymerization speed between a metal-organic framework (2-methylimidazole) and dopamine and metal ions (zinc ions) to realize two-dimensional-three-dimensional self-assembly, cooling, washing and drying to obtain the flower-shaped nano material (MOFs-PDA) with large aperture; secondly, carbonizing the MOFs-PDA nanoparticles to obtain the carbonized nanoenzyme with catalytic activity and large-aperture flower-like morphology based on the MOFs-PDA composite nanomaterial.
The composite nano material with the catalytic property is applied to preparation of peroxidase.
The use of the above-described composite nanomaterial having catalytic properties in the preparation of a drug delivery medium.
Further, the drug delivery media may be loaded with macromolecular bioparticles, including polypeptides, proteins, and/or nucleic acid molecules.
Metal-organic frameworks (MOFs), which are porous crystalline materials assembled from organic ligands and metal nodes, have a wide application prospect in biomedicine, particularly in drug delivery systems, due to their high drug loading, easy functionalization, good biodegradability and good biocompatibility. Compared with the defects that the traditional MOF material has small pore passages, is difficult to capture and carries biomacromolecules, the composite nano particles provided by the invention have the characteristics of unique large specific surface, rich pore passages and the like, and can be used as an excellent carrier of a nano-drug preparation. Is expected to solve the problems of biomedicine, especially the cancer treatment with nanometer medicine preparation in medicine transmission system.
Further, the drug delivery vehicle may be adapted for oral, pulmonary, and/or intravenous administration.
Advantageous effects
The invention successfully prepares and characterizes the carbonized nanometer enzyme based on MOFs-PDA composite nanometer materials with flower-shaped appearances, and the material has catalytic activity similar to peroxidase, so the material can also be called flower-shaped peroxidase.
The method comprises the steps of preparing large-aperture nano particles by regulating and controlling the amount of 2-methylimidazole, zinc nitrate hexahydrate and dopamine added into a mixed solution of methanol and water in a certain proportion at a certain temperature, and further exposing catalytic active sites by a carbonization means, so that the metal organic framework-polydopamine hybrid derivative carbide with a catalytic property and a macroporous structure is obtained.
In the prior art, certain limitations exist in the application direction of MOFs in catalysis, including that the internal pore diameter is about 2nm generally, and the limitations on rapid and effective diffusion and mass transfer of catalytic substrates and products are obvious, so that the catalytic activity is not ideal. On the other hand, the pore diameter can be improved to some extent by the high-temperature carbonization method, but the high-temperature carbonization method is often present in the form of hierarchical pores (6 to 15 nm) and has a small specific surface area. After long-term academic research and experimental exploration, research and development teams find that Dopamine (DA) molecules contain catechol groups and amino groups, can etch MOFs, and can form Polydopamine (PDA) coatings through self-polymerization under mild conditions. Meanwhile, abundant catechol groups in the PDA can be replaced and chelated with metal ions in the MOFs crystal to form a metal-polydopamine pore structure. On the other hand, in recent years, a three-dimensional porous structure nanomaterial formed by self-assembly of two-dimensional cells has attracted academic attention. The three-dimensional porous structure nano material assembled by the two-dimensional nano material can provide a large surface area-volume ratio and a large number of exposed catalytic active sites, so that the catalytic activity of the material can be improved. Meanwhile, the abundant pore space can be used for loading various biological function object molecules with different sizes. The research team of the invention further discovers that in the process of self-assembly of the PDA into a superstructure by the nanoparticles, the polyphenol modified nano modules can be interlocked to form a novel three-dimensional composite structure through the interface coordination interaction.
Inspired by this, the research team of the invention prepares a flower-shaped carbonized nanoenzyme based on MOFs-PDA composite nanomaterial with catalytic properties, which can solve at least one of the problems in the prior art. The flower-shaped carbonization nanometer enzyme based on the MOFs-PDA composite nanometer material, prepared by the invention, has uniform appearance and larger pore size structure, the pore size is about 40nm and far exceeds the common MOFs, the large pore size material is more beneficial to mass transfer/electron transfer in the catalysis process, and simultaneously has more reaction active sites, so the catalytic performance is high. In addition, the specific surface area of the flower-shaped carbonized nano enzyme based on the MOFs-PDA composite nano material prepared by the invention is about 300-400m 2 g -1 And the pore diameter is also higher than that obtained by the common high-temperature carbonization operation.
Finally, the method provided by the invention is simple and quick, the operation is convenient, the parameters of the preparation process are easy to regulate and control, and the prepared metal organic framework-polydopamine hybrid derivative carbide with the macroporous structure not only has the performance of nano enzyme, but also has the performance of loading object molecules, so that the application of the carbide in the field of drug delivery can be expanded.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below. It is obvious that the drawings in the following description are some embodiments of the invention, and that for a person skilled in the art, other drawings can be derived from them without inventive exercise.
FIG. 1 is a schematic diagram of a flower-like preparation method of a carbonized nanoenzyme based on MOFs-PDA composite nanomaterials;
FIG. 2 is a TEM photograph of flower-like carbonized nanoenzyme based on MOFs-PDA composite nanomaterial;
FIG. 3 is a scanning transmission electron microscope photograph of flower-like carbonized nanoenzymes based on MOFs-PDA composite nanomaterials;
FIG. 4 is a nitrogen adsorption isotherm diagram of flower-like carbonized nanoenzymes based on MOFs-PDA composite nanomaterials;
FIG. 5 is an XPS plot of flower-like carbonized nanoenzymes based on MOFs-PDA composite nanomaterials;
FIG. 6 is a diagram of the application of flower-like carbonized nanoenzymes based on MOFs-PDA composite nanomaterials in catalysis;
FIG. 7 is a graph of the application of flower-shaped carbonized nanoenzyme based on MOFs-PDA composite nanomaterial in protein adsorption.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention. It is to be understood that the embodiments described are only a few embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
It should be noted that, in this document, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrases "comprising a component of' 8230; \8230;" does not exclude the presence of another like element in a process, method, article, or apparatus that comprises the element.
As used in this specification, the term "about" typically means +/-5% of the stated value, more typically +/-4% of the stated value, more typically +/-3% of the stated value, more typically +/-2% of the stated value, even more typically +/-1% of the stated value, and even more typically +/-0.5% of the stated value.
In this specification, certain embodiments may be disclosed in a range of formats. It should be understood that this description of "within a certain range" is merely for convenience and brevity and should not be construed as an inflexible limitation on the scope of the disclosure. Accordingly, the description of a range should be considered to have specifically disclosed all the possible sub-ranges as well as individual numerical values within that range. For example, the range
The description should be read as having specifically disclosed subranges such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., as well as individual numbers within this range, e.g., 1,2,3,4,5, and 6. The above rules apply regardless of the breadth of the range.
Example one
FIG. 2 is a TEM image of flower-like carbonized nanoenzyme based on MOFs-PDA composite nanomaterial prepared in one embodiment of the present invention, and the nanomaterial prepared in the present invention has a uniform size of about 200nm.
FIG. 3 is a scanning transmission electron microscope photograph of flower-like carbonized nanoenzymes based on MOFs-PDA composite nanomaterials prepared by one embodiment of the present invention, and it can be seen from the photograph that the nanomaterials prepared by the present invention have uniform size, flower-like structure and good monodispersity.
FIG. 4 is a flower-like MOFs-PDA based composite nanomaterial prepared by one embodiment of the present inventionNitrogen adsorption isotherm of the carbonized nanoenzyme of the material. As can be seen from FIG. 4, the nano-material prepared by the invention has a mesoporous structure with a pore size of about 40nm and a specific surface area of 387.96m 2 g -1 。
FIG. 5 is an XPS plot of flower-like, MOFs-PDA based composite nanomaterials carbonized nanoenzymes prepared according to one embodiment of the present invention. As can be seen from fig. 5 (a), the prepared nanomaterial has four elements of C, N, O and Zn. As can be seen from fig. 5 (b), the N1s spectrum shows three peaks with binding energies of 397.7, 399.7 and 403.4eV, respectively, corresponding to pyridine N, pyrrole N and graphitized N, respectively as coordination centers of Zn atoms. As can be seen in FIG. 5 (c), the Zn2p spectrum shows two peaks at 1020.8 and 1043.8V, respectively assigned to the 2p of Zn species 3/2 And 2p 1/2 . Zinc species 2p 3/2 Is lower than the standard binding energy of ZnO (1022V), indicating that ZnO is not the predominant zinc species of C-NFs.
FIG. 6 is a diagram of the application of flower-like carbonized nanoenzyme based on MOFs-PDA composite nanomaterial prepared by one embodiment of the present invention in catalysis. As can be seen from fig. 6 (a), the nanomaterial prepared by the present invention can catalyze hydrogen peroxide to generate active oxygen species and hydroxyl radicals. As can be seen from fig. 6 (b) and (c), the ability to generate active oxygen at pH 5.0 (absorbance of 2.287 at 652 nm) was stronger than at pH 7.4 (0.008) or 6.5 (0.018), and the amount of active oxygen generated by the particles increased with the concentration of hydrogen peroxide. FIG. 6 (d) is a schematic diagram of the particles catalyzing hydrogen peroxide to generate active oxygen.
FIG. 7 is a diagram of the UV-VIS absorption spectrum of the flower-shaped carbonized nanoenzyme based on MOFs-PDA composite nanomaterial adsorbed onto the large-size guest molecule according to one embodiment of the present invention. As can be seen in FIG. 7, the prepared nanomaterial successfully carries protein (645. Mu.g/mg), and delivery of large-sized guest can be achieved.
Example two
This example provides an example of the preparation method of the present invention.
Step one, preparing 1g/mL zinc nitrate hexahydrate aqueous solution as mother liquor for later use.
Step two, 4.51mL of methanol and 1.956mL of deionized water were added to a 10mL single-neck flask. Adding 32mg of 2-methylimidazole and 10mg of dopamine, measuring 0.144mL of mother liquor of zinc nitrate hexahydrate in the step one, adding the mother liquor into the system, and stirring and reacting for 2 hours at 38 ℃.
After the reaction is finished, performing centrifugal separation on the obtained product at the rotation speed of 8000-11000 rpm/min for 3-5min to obtain a precipitate; washing the precipitate with anhydrous ethanol; and finally, placing the precipitate in a constant-temperature drying box at 60 ℃, and drying to obtain the MOF-PDA NFs nano-particles.
And step four, placing the MOF-PDA composite nano particles in a tubular furnace, introducing nitrogen, heating at a rate of 5 ℃/min, carbonizing at 800 ℃ for 1.5h, and obtaining black flower-shaped carbonized nano enzyme powder based on the MOFs-PDA composite nano materials.
EXAMPLE III
The method comprises the following steps: dispersing flower-shaped carbonized nano enzyme powder based on MOFs-PDA composite nano materials into 0.1M sodium acetate solution with the pH value of 5.0, wherein the final concentration is 1mg/mL for later use.
Step two: 3,3', 5' -Tetramethylbenzidine (TMB) was dispersed in dimethyl sulfoxide (DMSO) solution to prepare a mother liquor with a concentration of 10mg/mL for use.
Step three: taking 0.03mL of the mother solution of the particles in the first step into a 2mL centrifuge tube, adding 0.01mL of TMB (10 mg/mL) in the second step, and finally adding H with different molar concentrations 2 O 2 (50. Mu.M, 100. Mu.M, 500. Mu.M, 1mM and 2 mM).
Step four: incubating the mixed system of 1mL obtained in step three for 10min, and measuring absorbance values at 370nm and 652 nm.
Example four
The method comprises the following steps: flower-like carbonized nanoenzyme powder based on the MOFs-PDA composite nanomaterial was dispersed in a sodium acetate solution (0.1M, pH 5.0, pH 6.5, or pH 7.4) to a final concentration of 1mg/mL for use.
Step two: 3,3', 5' -Tetramethylbenzidine (TMB) was dispersed in Dimethylsulfoxide (DMSO) solution to prepare a mother liquor having a concentration of 10mg/mL, for use.
Step three: h with different pH values (0.1M, pH 5.0, pH 6.5 or pH 7.4) is prepared 2 O 2 So that the final mother liquor concentration was 2mM, ready for use.
Step three: 0.03mL of the pellet stock solution from step one was taken in a 2mL centrifuge tube, followed by 0.96mL of H at different pH values 2 O 2 (2 mM) and 0.01mL of TMB in step two (10 mg/mL).
Step four: incubating the mixed system of 1mL obtained in step three for 10min, and measuring absorbance values at 370nm and 652 nm.
EXAMPLE five
The method comprises the following steps: 1mg of doxorubicin hydrochloride and 1mg of apoferritin were weighed, 2mL of glycine-hydrochloric acid buffer (pH 3.0) was added, the mixture was vortexed for 10min, and then the pH was slowly adjusted to 7.4 with NaOH (1M).
Step two: dialyzing the product obtained in step one against a dialysis bag having a molecular weight of 1000 overnight.
Step three: and (4) weighing 1mg of flower-shaped carbonized nanoenzyme powder based on the MOFs-PDA composite nanomaterial, adding the flower-shaped carbonized nanoenzyme powder into the solution obtained in the step two, and uniformly mixing the flower-shaped carbonized nanoenzyme powder for 24 hours in a rotating manner.
Step four: the product was centrifuged at 11000rpm/min for 5min, the supernatant discarded, and washed 3 times with triple distilled water to remove free apoferritin.
While the present invention has been described with reference to the particular illustrative embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but is intended to cover various modifications, equivalent arrangements, and equivalents thereof, which may be made by those skilled in the art without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (6)
1. Use of a composite nanomaterial having catalytic properties in the preparation of a drug delivery medium capable of supporting macromolecular biological particles, including polypeptides, proteins and/or nucleic acid molecules; the composite nano material with catalytic property is a two-dimensional nano sheet formed by ZIF series metal organic framework materialsTaking polydopamine as a cross-linking agent to etch and perform metal ion replacement chelation on the two-dimensional nanosheets to obtain a three-dimensional metal organic framework-polydopamine pore structure, and carbonizing at high temperature to enable the polydopamine to have catalytic active sites; the catalytically active sites comprise Zn-Nx and/or Co-Nx; the composite nano material is in the shape of particles with flower-like structures, and the particle size of the particles is in the range of 50nm-5 mu m; the specific surface area of the composite nano material is 300-400m 2 g −1 The surface of the material also has a mesoporous structure with the aperture size of 20-50nm.
2. The use of claim 1, wherein the composite nanomaterial with catalytic properties is capable of participating in a redox reaction, and is capable of catalyzing hydrogen peroxide to generate active oxygen under acidic conditions, and the amount of generated active oxygen is directly proportional to the concentration of hydrogen peroxide.
3. The use according to claim 1, wherein the method for preparing the composite nanomaterial with catalytic properties comprises: the method comprises the steps of adopting zeolite imidazole ester framework material-8, 2-methylimidazole and zinc nitrate hexahydrate, firstly heating and stirring the 2-methylimidazole, the zinc nitrate hexahydrate and dopamine in a mixed solution of methanol and water to form a two-dimensional nanostructure, and then enabling the two-dimensional nanostructure to be self-assembled to form a three-dimensional structure by utilizing the capability of forming coordination bonds by poly-dopamine; the mass ratio of the 2-methylimidazole to the zinc nitrate hexahydrate to the dopamine is 20-40; finally, the material is prepared by high-temperature carbonization operation at 800 ℃.
4. The use according to claim 3, wherein the volume ratio of methanol to water is from 3 to 5.
5. The use of claim 3, wherein the high temperature carbonization operation is to obtain the composite nanomaterial with catalytic property by carbonizing at a temperature rising rate of 5-10 ℃/min to a final temperature of 800 ℃ for 1-2h under the condition of filling nitrogen.
6. The use of claim 1, wherein the drug delivery vehicle is suitable for oral administration, pulmonary administration, and/or intravenous administration.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011316506.5A CN112337499B (en) | 2020-11-20 | 2020-11-20 | Composite nano material with catalytic property, preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011316506.5A CN112337499B (en) | 2020-11-20 | 2020-11-20 | Composite nano material with catalytic property, preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112337499A CN112337499A (en) | 2021-02-09 |
| CN112337499B true CN112337499B (en) | 2023-01-31 |
Family
ID=74364424
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011316506.5A Active CN112337499B (en) | 2020-11-20 | 2020-11-20 | Composite nano material with catalytic property, preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112337499B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113430189B (en) * | 2021-06-24 | 2023-06-13 | 天津工业大学 | Trypsin co-embedded nanoflower catalytic membrane with embedded structure and preparation method and application thereof |
| CN114306382B (en) * | 2022-03-11 | 2022-11-11 | 南京大学 | Copper-based nanoenzyme as well as preparation method and application thereof |
| CN114652844B (en) * | 2022-04-13 | 2023-10-20 | 南京大学 | Preparation method and application of nano assembly material based on bionics design |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107876093A (en) * | 2017-11-29 | 2018-04-06 | 广西大学 | A kind of method of metal state in alkaline N regulation and control metal-carbide organic framework material |
| CN109399603A (en) * | 2018-11-05 | 2019-03-01 | 大连理工大学 | A method of supercapacitor N doping porous charcoal is prepared using metal organic framework compound |
| CN109607512A (en) * | 2019-01-31 | 2019-04-12 | 吉林大学 | It is a kind of to pass through the pyrolysis standby carbon quantum dot of system with molecular sieve for preparing and its in the application of hydrogen peroxide context of detection |
| CN109939718A (en) * | 2019-04-15 | 2019-06-28 | 中国科学院化学研究所 | A kind of monatomic catalyst and the preparation method and application thereof with high catalytic activity |
| CN110342487A (en) * | 2019-06-27 | 2019-10-18 | 浙江工业大学 | Preparation method of polydopamine modified MOF derived carbon molecular sieve |
| CN110819338A (en) * | 2019-10-11 | 2020-02-21 | 重庆大学 | Composite fluorescent particle protected by super-hydrophobic shell layer and preparation method thereof |
| CN111537577A (en) * | 2020-03-13 | 2020-08-14 | 郑州轻工业大学 | Metal-organic framework graphene analogue and preparation method thereof, aptamer sensor and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102676640B (en) * | 2011-03-10 | 2014-11-26 | 国家纳米科学中心 | Catalytic composite and visual detection method |
-
2020
- 2020-11-20 CN CN202011316506.5A patent/CN112337499B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107876093A (en) * | 2017-11-29 | 2018-04-06 | 广西大学 | A kind of method of metal state in alkaline N regulation and control metal-carbide organic framework material |
| CN109399603A (en) * | 2018-11-05 | 2019-03-01 | 大连理工大学 | A method of supercapacitor N doping porous charcoal is prepared using metal organic framework compound |
| CN109607512A (en) * | 2019-01-31 | 2019-04-12 | 吉林大学 | It is a kind of to pass through the pyrolysis standby carbon quantum dot of system with molecular sieve for preparing and its in the application of hydrogen peroxide context of detection |
| CN109939718A (en) * | 2019-04-15 | 2019-06-28 | 中国科学院化学研究所 | A kind of monatomic catalyst and the preparation method and application thereof with high catalytic activity |
| CN110342487A (en) * | 2019-06-27 | 2019-10-18 | 浙江工业大学 | Preparation method of polydopamine modified MOF derived carbon molecular sieve |
| CN110819338A (en) * | 2019-10-11 | 2020-02-21 | 重庆大学 | Composite fluorescent particle protected by super-hydrophobic shell layer and preparation method thereof |
| CN111537577A (en) * | 2020-03-13 | 2020-08-14 | 郑州轻工业大学 | Metal-organic framework graphene analogue and preparation method thereof, aptamer sensor and preparation method thereof |
Non-Patent Citations (9)
| Title |
|---|
| A facile one-pot synthesis of hemin/ZIF-8 composite as mimetic peroxidase;DanlinLi et al;《MATERIALS LETTERS》;20160426;第178卷;第49页左栏实验 * |
| A ZIF-triggered rapid polymerization of dopamine renders Co/N-codoped cage-in-cage porous carbon for highly efficient oxygen reduction and evolution;Teng Wang et al;《Nano Energy》;20201014;第79卷;第9页左栏实验 * |
| Cobalt-Iron mixed-metal-organic framework (Co3Fe-MMOF) as peroxidase mimic for highly sensitive enzyme-linked immunosorbent assay (ELISA) detection of Aeromonas hydrophila;Dongpo Xu et al;《Microchemical Journal》;20191230;第154卷;全文 * |
| Metal organic framework-derived hollow cactus-like carbon sheets for oxygen reduction;Ming Zhang et al;《J. Mater. Chem. A》;20190820;第7卷;第20162-20168页 * |
| Teng Wang et al.A ZIF-triggered rapid polymerization of dopamine renders Co/N-codoped cage-in-cage porous carbon for highly efficient oxygen reduction and evolution.《Nano Energy》.2020,第79卷全文. * |
| Ultrathin ZIF-67 nanosheets as a colorimetric biosensing platform for peroxidase-like catalysis;Shujuan Wang et al;《Analytical and Bioanalytical Chemistry》;20180901;摘要、第1页左栏 * |
| 基于铁钴的纳米材料模拟酶特性及其生物分析应用探究;赵佳;《中国优秀博硕士学位论文全文数据库(硕士) 基础科学辑》;20200115(第1期);全文 * |
| 聚多巴胺/药物纳米复合物的构筑及其在骨缺损修复中的应用;王璐 等;《2017全国口腔生物医学学术年会论文汇编》;20171013;第161-162页 * |
| 过渡金属及氮共掺杂的多孔碳氧还原催化剂的制备与性能研究;周妮;《中国优秀博硕士学位论文全文数据库(硕士) 工程科技Ⅰ辑》;20200115(第1期);全文 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112337499A (en) | 2021-02-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112337499B (en) | Composite nano material with catalytic property, preparation method and application | |
| Ma et al. | Application of MOF-based materials in electrochemical sensing | |
| Liu et al. | Metal-organic framework-based materials as an emerging platform for advanced electrochemical sensing | |
| Wang et al. | Recent progress in metal-organic frameworks-based hydrogels and aerogels and their applications | |
| Nadar et al. | Magnetic-metal organic framework (magnetic-MOF): A novel platform for enzyme immobilization and nanozyme applications | |
| Xu et al. | Pt@ UiO-66 heterostructures for highly selective detection of hydrogen peroxide with an extended linear range | |
| Liu et al. | Metal-organic framework composites as green/sustainable catalysts | |
| Ma et al. | Combination of metal-organic frameworks (MOFs) and covalent organic frameworks (COFs): Recent advances in synthesis and analytical applications of MOF/COF composites | |
| El Hankari et al. | Biopolymer@ metal-organic framework hybrid materials: a critical survey | |
| Zhu et al. | Metal–organic framework composites | |
| Liu et al. | The applications of metal− organic frameworks in electrochemical sensors | |
| Kumar et al. | Modern progress in metal-organic frameworks and their composites for diverse applications | |
| Morris et al. | Role of modulators in controlling the colloidal stability and polydispersity of the UiO-66 metal–organic framework | |
| Maity et al. | Dendritic fibrous nanosilica for catalysis, energy harvesting, carbon dioxide mitigation, drug delivery, and sensing | |
| Zhang et al. | Hierarchical mesoporous metal–organic frameworks encapsulated enzymes: Progress and perspective | |
| Li et al. | Metal–organic framework composites: from fundamentals to applications | |
| Zhu et al. | Reconstructing hydrophobic ZIF-8 crystal into hydrophilic hierarchically-porous nanoflowers as catalyst carrier for nonenzymatic glucose sensing | |
| Zhou et al. | Selenium-functionalized metal-organic frameworks as enzyme mimics | |
| Figueroa‐Quintero et al. | Post‐synthetic surface modification of metal–organic frameworks and their potential applications | |
| Guo et al. | The effect of Co and N of porous carbon-based materials fabricated via sacrificial templates MOFs on improving DA and UA electrochemical detection | |
| Cao et al. | Synthesis of yolk/shell heterostructures MOF@ MOF as biomimetic sensing platform for catechol detection | |
| Deng et al. | Encapsulation of platinum nanoparticles into a series of zirconium-based metal-organic frameworks: Effect of the carrier structures on electrocatalytic performances of composites | |
| CN109894149A (en) | A kind of composite nanostructure catalyst and its preparation and application | |
| Mallakpour et al. | Emerging new-generation hybrids based on covalent organic frameworks for industrial applications | |
| Xu et al. | MIL-100 (Fe) metal–organic framework nanospheres embedded in graphene matrixes for xanthine fluorescence sensing |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |